Process for the epoxidation of an organic compound with oxygen or an oxygen-delivering compounds using catalysts containing metal-organic frame-work materials

ABSTRACT

The present invention relates to a process for the reaction of at least one organic compound with one oxygen-delivering substance, for example a hydroperoxide, in the presence of at least one catalyst containing a metal-organic framework material comprising pores and a metal ion and an at least bidentate organic compound, said bidentate organic compound being coordinately bound to the metal ion. Further, the present invention is directed to the products being obtainable by the process according to the invention.

The present invention relates to a process for the epoxidation of at least one organic compound with oxygen or an oxygen-delivering compound, in the presence of at least one catalyst containing a metal-organic framework material comprising pores and a metal ion and an at least bidentate organic compound, said bidentate organic compound being coordinately bound to the metal ion. Further, the present invention is directed to the products being obtainable by the process according to the invention.

Reactions of organic compounds with oxidizing agents as hydroperoxides are well known in the prior art, for example from DE 100 55 652.3 and further patent applications of the present applicant, such as DE 100 32 885.7, DE 100 32 884.9 or DE 100 15 246.5.

The state of the art for catalysts used in epoxidation reactions is given by materials containing zeolites, in particular catalysts which comprise a titanium-, vanadium-, chromium-, niobium- or zirconium-containing zeolite as a porous oxidic material. Such catalysts are described, for example, in WO 00/07965.

In a promising novel and alternative strategy to create micro- and/or mesoporous catalytically active materials, metal ions and molecular organic building blocks are used to form so-called metal-organic frameworks (MOFs). The metal-organic framework materials as such are described, for example, in. U.S. Pat. No. 5,648,508, EP-A-0 709 253, M. O'Keeffe et al., J. Sol. State Chem., 152 (2000) p. 3-20, H. Li et al., Nature 402 (1999) p. 276 seq., M. Eddaoudi et al., Topics in Catalysis 9 (1999) p. 105-111,B. Chen et al., Science 291 (2001) p. 1021-23. Among the advantages of these novel materials, in particular for applications in catalysis, are the following:

(i) larger pore sizes can be realized than for the zeolites used presently

(ii) the internal surface area is larger than for porous materials used presently

(iii) pore size and/or channel structure can be tailored over a large range

(iv) the organic framework components forming the internal surface can be functionalized easily.

However, these novel porous materials have only been described as such. The use of these catalytically active materials in reactions of technical importance, in particular for epoxidation reactions, has not been disclosed yet.

It is an object of the present invention to provide a catalyst for the reaction of organic compounds with oxygen and/or oxygen-delivering compounds, wherein the catalyst for said reaction contains a novel material, in addition to, or instead of, catalytic materials according to the prior art, particularly in addition to, or instead of, zeolites.

This object is solved by providing a process for the epoxidation of at least one organic compound with oxygen and/or at least one oxygen-delivering compound in the presence of a catalyst, wherein said catalyst contains a metal-organic framework material comprising pores and at least one metal ion and at least one at least bidentate organic compound, which is coordinately bound to said metal ion.

As epoxidation agents, oxygen and oxygen-delivering compounds can be used. This includes but is not limited to ozone, water, oxidizing enzymes, reactive oxides, such as permanganates, chromic oxide, nitric oxide and the like. If oxygen is used, the gas may be mixed with other reactive gases and/or inert gases. Preferred are hydroperoxides known from the prior art which are suitable for the reaction of the organic compound. Mixtures of at least two of the aforementioned epoxidation agents are included as well. The generic formula of a hydroperoxide can be given as R—O—O—H. In principle, any organic or inorganic entity known to the expert in the field may be used as the group “R”. Examples of such hydroperoxides are tertbutyl hydroperoxide, ethylbenzene hydroperoxide, and cumenehydroperoxide. In the present invention, preference is given to using hydrogen peroxide as hydrol peroxide. The present invention therefore also provides a process as described above, in which the hydroperoxide used is hydrogen peroxide. Preference is given to using an aqueous hydrogen peroxide solution. The hydrogen peroxide, or any hydroperoxide for that matter, can be either prepared outside the reaction or by starting from hydrogen and oxygen, or other suitable components, in situ within the reaction.

With respect to epoxidation reactions, DE 100 55 652.3, DE 100 32 885.7, DE 100 32 884.9, DE 100 15 246.5, DE 199 36 547.4, DE 199 26 725.1, DE 198 47 629.9, DE 198 35 907.1, DE 197 23 950.1 are fully encompassed within the content of the present application with respect to their respective content.

Other known processes for epoxidation reactions are not excluded from the present application, and are, for example, described in Weissermel, Arpe “Industrielle Organische Chemie”, publisher VCH, Weinheim, 4^(th) Ed., pages 288 to 318 and in U. Onken, Anton Behr, “Chemische Prozesskunde”, Vol. 3, Thieme, 1996, pages 303 to 305 as well as Weissernel, Arpe “Industrial Organic Chemistry”, 5^(th) Ed., Wiley, 1998, pages 159 to 181.

Among the reactions which are possible in the process of the present invention, the following are mentioned by way of example and without limiting the general scope of the present invention:

the epoxidation of olefins, e.g. the preparation of propylene oxide from propylene and H₂O₂ or from propylene and mixtures which provide H₂O₂ in situ;

hydroxylations such as the hydroxylation of monocyclic, bicyclic or polycyclic aromatics to give monosubstituted, disubstituted or higher-substituted hydroxyaromatics, for example the reaction of phenol and H₂O₂, or of phenol and mixtures which provide H₂O₂ in situ, to form hydroquinone;

oxime formation from ketones in the presence of H₂O₂, or mixtures which provide H₂O₂ in situ, and ammonia (ammonoximation), for example the preparation of cyclohexanone oxime from cyclohexanone;

the Baeyer-Villiger oxidation.

In the process of the present invention, organic compounds which have at least one C—C double bond are epoxidized.

Examples of such organic compounds having at least one C—C double bond are the following alkenes: ethene, propene, 1-butene, 2-butene, isobutene, butadiene, pentene, piperylene, hexenes, hexadienes, heptenes, octenes, diisobutene, trimethylpentene, nonenes, dodecene, tridecene, tetradecene to eicosene, tripropene and tetrapropene, polybutadienes, polyisobutenes, isoprenes, terpenes, geraniol, linalool, linalyl acetate, methylenecyclopropane, cyclopentene, cyclohexene, norbornene, cycloheptene, vinylcyclohexane, vinyloxiran, vinylcyclohexene, styrene, cyclooctene, cyclooctadiene, vinylnorbornene, indene, tetrahydroindene, methylstyrene, dicyclopentadiene, dinvinylbenzene, cyclododecene, cyclododecatriene, stilbene, diphenylbutadiene, vitamin A, beta-carotene, vinylidene fluoride, allyl halides, crotyl chloride, methallyl chloride, dichlorobutene, allyl alcohol, methallyl alcohol, butenols, butenediols, cyclopentenediols, pentenols, octadienols, tridecenols, unsaturated steroids, ethoxyethene, isoeugenol, anethole, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, vinylacetic acid, unsaturated fatty acids such as oleic acid, linoleic acid, palmitic acid, naturally occurring fats and oils.

The process of the present invention is preferably carried out using alkenes having from 2 to 8 carbon atoms. Particular preference is given to reacting ethene, propylene and butene.

As has been mentioned above, metal-organic framework materials as such are described in, for example, U.S. Pat. No. 5,648,508, EP-A-0 709 253, M. O'Keeffe et al., J Sol. State Chem., 152 (2000) p. 3-20, H. Li et al., Nature 402 (1999) p. 276 seq., M. Eddaoudi et al., Topics in Catalysis 9 (1999) p. 105-111, B. Chen et al., Science 291 (2001) p. 1021-23. An inexpensive way for the preparation of said materials is the subject of DE 10111230.0. The content of these publications, to which reference is made herein, is fully incorporated in the content of the present application.

The catalyst used in the present invention contains at least one of the metal-organic framework material, for example one of the materials described below.

The metal-organic framework materials, as used in the present invention, comprise pores, particularly micro- and/or mesopores. Micropores are defined as being pores having a diameter of 2 nm or below and mesopores as being pores having a diameter in the range of above 2 nm to 50 nm, respectively, according to the definition given in Pure Applied Chem. 45, p. 71 seq., particularly on p. 79 (1976). The presence of the micro- and/or mesopores can be monitored by sorption measurements for determining the capacity of the metal-organic framework materials to take up nitrogen at 77 K according to DIN 66131 and/or DIN 66134.

For example, a type-I-form of the isothermal curve indicates the presence of micropores [see, for example, paragraph 4 of M. Eddaoudi et al., Topics in Catalysis 9 (1999)]. In a preferred embodiment, the specific surface area, as calculated according to the Langmuir model (DIN 66131, 66134) preferably is above 5 m²/g, further preferred above 10 m²/g, more preferably above 50 m²/g, particularly preferred above 500 m²/g and may increase into the region of to above 3000 m²/g.

As to the metal component within the framework material that is to be used according to the present invention, particularly to be mentioned are the metal ions of the main group elements and of the subgroup elements of the periodic system of the elements, namely of the groups Ia, Ia, IIIa, IVa to VIIIa and Ib to VIb. Among those metal components, particular reference is made to Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, and Bi, more preferably to Zn, Cu, Ni, Pd, Pt, Ru, Rh and Co. As to the metal ions of these elements, particular reference is made to: Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Sc³⁺, Y³⁺, Ti⁴⁺, Zr⁴⁺, Hf⁴⁺, V⁴⁺, V³⁺, V²⁺, Nb³⁺, Ta³⁺, Cr³⁺, Mo³⁺, W³⁺, Mn³⁺, Mn²⁺, Re³⁺, Re²⁺, Fe³⁺, Fe²⁺, Ru³⁺, Ru²⁺, Os³⁺, Os²⁺, Co³⁺, Co²⁺, Rh²⁺, Rh⁺, Ir²⁺, Ir⁺, Ni²⁺, Ni⁺, Pd²⁺, Pd⁺, Pt²⁺, Pt⁺, Cu²⁺, Cu⁺, Ag⁺, Au⁺, Zn²⁺, Cd²⁺, Hg²⁺, Al³⁺, Ga³⁺, In³⁺, Tl³⁺, Si⁴⁺, Si²⁺, Ge⁴⁺, Ge²⁺, Sn⁴⁺, Sn²⁺, Pb⁴⁺, Pb²⁺, As⁵⁺, As³⁺, As⁺, Sb⁵⁺, Sb³⁺, Sb⁺, Bi⁵⁺, Bi³⁺ and Bi⁺.

With regard to the preferred metal ions and further details regarding the same, particular reference is made to: EP-A 0 790 253, particularly to p. 10, 1. 8-30, section “The Metal Ions”, which section is incorporated herein by reference.

In addition to the metal salts disclosed in EP-A 0 790 253 and U.S. Pat. No. 5,648,508, other metallic compounds can be used, such as sulfates, phosphates and other complex counter-ion metal salts of the main- and subgroup metals of the periodic system of the elements. Metal oxides, mixed oxides and mixtures of metal oxides and/or mixed oxides with or without a defined stoichiometry are preferred. All of the above mentioned metal compounds can be soluble or insoluble and they may be used as starting material either in form of a powder or as a shaped body or as any combination thereof.

As to the at least bidentate organic compound, which is capable to coordinate with the metal ion, in principle all compounds can be used which are suitable for this purpose and which fulfill the above requirements of being at least bidentate. Said organic compound must have at least two centers, which are capable to coordinate with the metal ions of a metal salt, particularly with the metals of the aforementioned groups. With regard to the at least bidentate organic compound, specific mention is to be made of compounds having

i) an alkyl group substructure, having from 1 to 10 carbon atoms,

ii) an aryl group substructure, having from 1 to 5 phenyl rings,

iii) an alkyl or aryl amine substructure, consisting of alkyl groups having from 1 to 10 carbon atoms or aryl groups having from 1 to 5 phenyl rings,

said substructures having bound thereto at least one at least bidentate functional group “X”, which is covalently bound to the substructure of said compound, and wherein X is selected from the group consisting of

CO₂H, CS₂H, NO₂, SO₃H, Si(OH)₃, Ge(OH)₃, Sn(OH)₃, Si(SH)₄, Ge(SH)₄, Sn(SH)₃, PO₃H, AsO₃H, AsO₄H, P(SH)₃, As(SH)₃, CH(RSH)₂, C(RSH)₃, CH(RNH₂)₂, C(RNH₂)₃, CH(ROH)₂, C(ROH)₃, CH(RCN)₂, C(RCN)₃, wherein R is an alkyl group having from 1 to 5 carbon atoms, or an aryl group consisting of 1 to 2 phenyl rings, and CH(SH)₂, C(SH)₃, CH(NH₂)₂, C(NH₂)₂, CH(OH)₂, C(OH)₃, CH(CN)₂ and C(CN)₃.

Particularly to be mentioned are substituted or unsubstituted, mono- or polynuclear aromatic di-, tri- and tetracarboxylic acids and substituted or unsubstituted, aromatic, at least one hetero atom comprising aromatic di-, tri- and tetracarboxylic acids, which have one or more nuclei.

A preferred ligand is 1,3,5-benzene tricarboxylate (BCT). Further preferred ligands are ADC (acetylene dicarboxylate), NDC (naphtalen dicarboxylate), BDC (benzene dicarboxylate), ATC (adamantane tetracarboxylate), BTC (benzene tri-carboxylate), BTB (benzene tribenzoate), MTB (methane tetrabenzoate) and ATB (adamantane tribenzoate).

Besides the at least bidentate organic compound, the framework material as used in accordance with the present invention may also comprise one or more mono-dentate ligand(s), which is/are preferably selected from the following mono-dentate substances and/or derivatives thereof:

a. alkyl amines and their corresponding alkyl ammonium salts, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms (and their corresponding ammonium salts);

b. aryl amines and their corresponding aryl ammonium salts having from 1 to 5 phenyl rings;

c. alkyl phosphonium salts, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;

d. aryl phosphonium salts, having from 1 to 5 phenyl rings;

e. alkyl organic acids and the corresponding alkyl organic anions (and salts) containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;

f. aryl organic acids and their corresponding aryl organic anions and salts, having from 1 to 5 phenyl rings;

g. aliphatic alcohols, containing linear, branched, or cyclic aliphatic groups, having from 1 to 20 carbon atoms;

h. aryl alcohols having from 1 to 5 phenyl rings;

i. inorganic anions from the group consisting of: sulfate, nitrate, nitrite, sulfite, bisulfite, phosphate, hydrogen phosphate, dihydrogen phosphate, diphosphate, triphosphate, phosphite, chloride, chlorate, bromide, bromate, iodide, iodate, carbonate, bicarbonate, and the corresponding acids and salts of the aforementioned inorganic anions,

j. ammonia, carbon dioxide, methane, oxygen, ethylene, hexane, benzene, toluene, xylene, chlorobenzene, nitrobenzene, naphthalene, thiophene, pyridine, acetone, 1-2-dichloroethane, methylenechloride, tetrahydrofuran, ethanolamine, triethylamine and trifluoromethylsulfonic acid.

Further details regarding the at least bidentate organic compounds and the mono-dentate substances, from which the ligands of the framework material as used in the present application are derived, can be taken from EP-A 0 790 253, whose respective content is incorporated into the present application by reference.

Within the present application, framework materials of the kind described herein, which comprise Zn²⁺ as a metal ion and ligands derived from terephthalic acid as the bidentate compound, are particularly preferred. Said framework materials are known as MOF-5 in the literature.

Further metal ions and at least bidentate organic compounds and mono-dentate substances, which are respectively useful for the preparation of the framework materials used in the present invention as well as processes for their preparation are particularly disclosed in EP-A 0 790 253, U.S. Pat. No. 5,648,508 and DE 10111230.0.

As solvents, which are particularly useful for the preparation of MOF-5, in addition to the solvents disclosed in the above-referenced literature, dimethyl formamide, diethyl formamide and N-methylpyrollidone, alone, in combination with each other or in combination with other solvents may be used. Within the preparation of the framework materials, particularly within the preparation of MOF-5, the solvents and mother liquors are recycled after crystallization in order to save costs and materials.

The pore sizes of the metal-organic framework can be adjusted by selecting suitable organic ligands and/or bidendate compounds (=linkers). Generally, the larger the linker, the larger the pore size. Any pore size that is still supported by a the metal-organic framework in the absence of a host and at temperatures of at least 200° C. is conceivable. Pore sizes ranging from 0,2 nm to 30 nm are preferred, with pore sizes ranging from 0,3 nm to 3 nm being particularly preferred.

In the following, examples of metal-organic framework materials (MOFs) are given to illustrate the general concept given above. These specific examples, however, are not meant to limit the generality and scope of the present application.

By way of example, a list of metal-organic framework materials already synthesized and characterized is given below. This also includes novel isoreticular metal organic framework materials (IR-MOFs), which may be used in the context of the present application. Such materials having the same framework topology while displaying different pore sizes and crystal densities are described, for example in M. Eddouadi et al., Science 295 (2002) 469, whose respective content is incorporated into the present application by reference

The solvents used are of particular importance for the synthesis of these materials and are therefore mentioned in the table. The values for the cell parameters (angles α, β and γ as well as the spacings a, b and c, given in Angstrom) have been obtained by x-ray diffraction and represent the space group given in the table as well.

Ingredients molar ratios Space MOF-n M + L Solvents α β γ a b c Group MOF-0 Zn(NO₃)₂.6H₂O ethanol 90 90 120 16.711 16.711 14.189 P6(3)/Mcm H₃(BTC) MOF-2 Zn(NO₃)₂.6H₂O DMF 90 102.8 90 6.718 15.49 12.43 P2(1)/n (0.246 mmol) toluene H₂(BDC) (0.241 mmol) MOF-3 Zn(NO₃)₂.6H₂O DMF 99.72 111.11 108.4 9.726 9.911 10.45 P-1 (1.89 mmol) MeOH H₂(BDC) (1.93 mmol) MOF-4 Zn(NO₃)₂.6H₂O ethanol 90 90 90 14.728 14.728 14.728 P2(1)3 (1.00 mmol) H₃(BTC) (0.5 mmol) MOF-5 Zn(NO₃)₂.6H₂O DMF 90 90 90 25.669 25.669 25.669 Fm-3m (2.22 mmol) chloro- H₂(BDC) benzene (2.17 mmol) MOF-38 Zn(NO₃)₂.6H₂O DMF 90 90 90 20.657 20.657 17.84 14 cm (0.27 mmol) chloro- H₃(BTC) benzene (0.15 mmol) MOF-31 Zn(NO₃)₂.6H₂O ethanol 90 90 90 10.821 10.821 10.821 Pn(-3)m Zn(ADC)₂ 0.4 mmol H₂(ADC) 0.8 mmol MOF-12 Zn(NO₃)₂.6H₂O ethanol 90 90 90 15.745 16.907 18.167 Pbca Zn₂(ATC) 0.3 mmol H₄(ATC) 0.15 mmol MOF-20 Zn(NO₃)₂.6H₂O DMF 90 92.13 90 8.13 16.444 12.807 P2(1)/c ZnNDC 0.37 mmol chloro- H₂NDC benzene 0.36 mmol MOF-37 Zn(NO₃)₂.6H₂O DEF 72.38 83.16 84.33 9.952 11.576 15.556 P-1 0.2 mmol chloro- H₂NDC benzene 0.2 mmol MOF-8 Tb(NO₃)₃.5H₂O DMSO 90 115.7 90 19.83 9.822 19.183 C2/c Tb₂(ADC) 0.10 mmol MeOH H₂ADC 0.20 mmol MOF-9 Tb(NO₃)₃.5H₂O DMSO 90 102.09 90 27.056 16.795 28.139 C2/c Tb₂(ADC) 0.08 mmol H₂ADB 0.12 mmol MOF-6 Tb(NO₃)₃.5H₂O DMF 90 91.28 90 17.599 19.996 10.545 P21/c 0.30 mmol MeOH H₂(BDC) 0.30 mmol MOF-7 Tb(NO₃)₃.5H₂O H₂O 102.3 91.12 101.5 6.142 10.069 10.096 P-1 0.15 mmol H₂(BDC) 0.15 mmol MOF-69A Zn(NO₃)₂.6H₂O DEF 90 111.6 90 23.12 20.92 12 C2/c 0.083 mmol H₂O₂ 4,4‘BPDC MeNH₂ 0.041 mmol MOF-69B Zn(NO₃)₂.6H₂O DEF 90 95.3 90 20.17 18.55 12.16 C2/c 0.083 mmol H₂O₂ 2,6-NCD MeNH₂ 0.041 mmol MOF-11 Cu(NO₃)₂.2.5H₂O H₂O 90 93.86 90 12.987 11.22 11.336 C2/c Cu₂(ATC) 0.47 mmol H₂ATC 0.22 mmol MOF-11 90 90 90 8.4671 8.4671 14.44 P42/mmc Cu₂(ATC) dehydr. MOF-14 Cu(NO₃)₂.2.5H₂O H₂O 90 90 90 26.946 26.946 26.946 Im-3 Cu₃(BTB) 0.28 mmol DMF H₃BTB EtOH 0.052 mmol MOF-32 Cd(NO₃)₂.4H₂O H₂O 90 90 90 13.468 13.468 13.468 P(-4)3m Cd(ATC) 0.24 mmol NaOH H₄ATC 0.10 mmol MOF-33 ZnCl₂ H₂O 90 90 90 19.561 15.255 23.404 Imma Zn₂(ATB) 0.15 mmol DMF H₄ATB EtOH 0.02 mmol MOF-34 Ni(NO₃)₂.6H₂O H₂O 90 90 90 10.066 11.163 19.201 P2₁2₁2₁ Ni(ATC) 0.24 mmol NaOH H₄ATC 0.10 mmol MOF-36 Zn(NO₃)₂.4H₂O H₂O 90 90 90 15.745 16.907 18.167 Pbca Zn₂(MTB) 0.20 mmol DMF H₄MTB 0.04 mmol MOF-39 Zn(NO₃)₂4H₂O H₂O 90 90 90 17.158 21.591 25.308 Pnma Zn₃O(HBTB) 0.27 mmol DMF H₃BTB EtOH 0.07 mmol NO305 FeCl₂.4H₂O DMF 90 90 120 8.2692 8.2692 63.566 R-3c 5.03 mmol formic acid 86.90 mmol NO306A FeCl₂.4H₂O DEF 90 90 90 9.9364 18.374 18.374 Pbcn 5.03 mmol formic acid 86.90 mmol NO29 Mn(Ac)₂.4H₂O DMF 120 90 90 14.16 33.521 33.521 P-1 MOF-0 like 0.46 mmol H₃BTC 0.69 mmol BPR48 Zn(NO₃)₂6H₂O DMSO 90 90 90 14.5 17.04 18.02 Pbca A2 0.012 mmol toluene H₂BDC 0.012 mmol BPR69 Cd(NO₃)₂4H₂O DMSO 90 98.76 90 14.16 15.72 17.66 Cc B1 0.0212 mmol H₂BDC 0.0428 mmol BPR92 Co(NO₃)₂.6H₂O NMP 106.3 107.63 107.2 7.5308 10.942 11.025 P1 A2 0.018 mmol H₂BDC 0.018 mmol BPR95 Cd(NO₃)₂4H₂O NMP 90 112.8 90 14.460 11.085 15.529 P2(1)/n C5 0.012 mmol H₂BDC 0.36 mmol CuC₆H₄O₆ Cu(NO₃)₂.2.5H₂O DMF 90 105.29 90 15.259 14.816 14.13 P2(1)/c 0.370 mmol chloro- H₂BDC(OH)₂ benzene 0.37 mmol M(BTC) Co(SO₄)H₂O DMF Same as MOF-0 MOF-0 like 0.055 mmol H₃BTC 0.037 mmol Tb(C₆H₄O₆₎ Tb(NO₃)₃.5H₂O DMF 104.6 107.9 97.147 10.491 10.981 12.541 P-1 0.370 mmol chloro- H₂(C₆H₄O₆) benzene 0.56 mmol Zn(C₂O₄) ZnCl₂ DMF 9.0 120 90 9.4168 9.4168 8.464 P(-3)/m 0.370 mmol chloro- oxalic acid benzene 0.37 mmol Co(CHO) Co(NO₃)₂.5H₂O DMF 90 91.32 90 11.328 10.049 14.854 P2(1)/n 0.043 mmol formic acid 1.60 mmol Cd(CHO) Cd(NO₃)₂.4H₂O DMF 90 120 90 8.5168 8.5168 22.674 R-3c 0.185 mmol formic acid 0.15 mmol Cu(C₃H₂O₄) Cu(NO₃)₂.2.5H₂O DMF 90 90 90 8.366 8.366 11.919 P43 0.043 mmol malonic acid 0.192 mmol Zn₆(NDC)₅ Zn(NO₃)₂.6H₂O DMF 90 95.902 90 19.504 16.482 14.64 C2/m MOF-48 0.097 mmol chloro- 14 NDC benzene 0.069 mmol H₂O₂ MOF-47 Zn(NO₃)₂6H₂O DMF 90 92.55 90 11.303 16.029 17.535 P2(1)/c 0.185 mmol chloro- H₂(BDC[CH₃]₄) benzene 0.185 mmol H₂O₂ MO25 Cu(NO₃)₂.2.5H₂O DMF 90 112.0 90 23.880 16.834 18.389 P2(1)/c 0.084 mmol BPhDC 0.085 mmol Cu-Thio Cu(NO₃)₂.2.5H₂O DEF 90 113.6 90 15.4747 14.514 14.032 P2(1)/c 0.084 mmol thiophene dicarboxylic 0.085 mmol ClBDC1 Cu(NO₃)₂.2.5H₂O DMF 90 105.6 90 14.911 15.622 18.413 C2/c 0.084 mmol H₂(BDCCl₂) 0.085 mmol MOF-101 Cu(NO₃)₂.2.5H₂O DMF 90 90 90 21.607 20.607 20.073 Fm3m 0.084 mmol BrBDC 0.085 mmol Zn₃(BTC)₂ ZnCl₂ DMF 90 90 90 26.572 26.572 26.572 Fm-3m 0.033 mmol EtOH H₃BTC base 0.033 mmol added MOF-j Co(CH₃CO₂)₂.4H₂O H₂O 90 112.0 90 17.482 12.963 6.559 C2 (1.65 mmol) H₃(BZC) (0.95 mmol) MOF-n Zn(NO₃)₂.6H₂O ethanol 90 90 120 16.711 16.711 14.189 P6(3)/mcm H₃(BTC) PbBDC Pb(NO₃)₂ DMF 90 102.7 90 8.3639 17.991 9.9617 P2(1)/n (0.181 mmol) ethanol H₂(BDC) (0.181 mmol) Znhex Zn(NO₃)₂.6H₂O DMF 90 90 120 37.1165 37.117 30.019 P3(1)c (0.171 mmol) p-xylene H₃BTB ethanol (0.114 mmol) AS16 FeBr₂ DMF 90 90.13 90 7.2595 8.7894 19.484 P2(1)c 0.927 mmol anhydr. H₂(BDC) 0.927 mmol AS27-2 FeBr₂ DMF 90 90 90 26.735 26.735 26.735 Fm3m 0.927 mmol anhydr. H₃(BDC) 0.464 mmol AS32 FeCl₃ DMF 90 90 120 12.535 12.535 18.479 P6(2)c 1.23 mmol anhydr. H₂(BDC) ethanol 1.23 mmol AS54-3 FeBr₂ DMF 90 109.98 90 12.019 15.286 14.399 C2 0.927 anhydr. BPDC n-propanol 0.927 mmol AS61-4 FeBr₂ pyridine 90 90 120 13.017 13.017 14.896 P6(2)c 0.927 mmol anhydr. m-BDC 0.927 mmol AS68-7 FeBr₂ DMF 90 90 90 18.3407 10.036 18.039 Pca2₁ 0.927 mmol anhydr. m-BDC Pyridine 1.204 mmol Zn(ADC) Zn(NO₃)₂.6H₂O DMF 90 99.85 90 16.764 9.349 9.635 C2/c 0.37 mmol chloro- H₂(ADC) benzene 0.36 mmol MOF-12 Zn(NO₃)₂.6H₂O ethanol 90 90 90 15.745 16.907 18.167 Pbca Zn₂(ATC) 0.30 mmol H₄(ATC) 0.15 mmol MOF-20 Zn(NO₃)₂.6H₂O DMF 90 92.13 90 8.13 16.444 12.807 P2(1)/c ZnNDC 0.37 mmol chloro- H₂NDC benzene 0.36 mmol MOF-37 Zn(NO₃)₂.6H₂O DEF 72.38 83.16 84.33 9.952 11.576 15.556 P-1 0.20 mmol chloro- H₂NDC benzene 0.20 mmol Zn(NDC) Zn(NO₃)₂.6H₂O DMSO 68.08 75.33 88.31 8.631 10.207 13.114 P-1 (DMSO) H₂NDC Zn(NDC) Zn(NO₃)₂.6H₂O 90 99.2 90 19.289 17.628 15.052 C2/c H₂NDC Zn(HPDC) Zn(NO₃)₂.4H₂O DMF 107.9 105.06 94.4 8.326 12.085 13.767 P-1 0.23 mmol H₂O H₂(HPDC) 0.05 mmol Co(HPDC) Co(NO₃)₂.6H₂O DMF 90 97.69 90 29.677 9.63 7.981 C2/c 0.21 mmol H₂O/ H₂(HPDC) ethanol 0.06 mmol Zn₃(PDC)2.5 Zn(NO₃)₂.4H₂O DMF/ 79.34 80.8 85.83 8.564 14.046 26.428 P-1 0.17 mmol CIBz H₂(HPDC) H₂O/ 0.05 mmol TEA Cd₂(TPDC)2 Cd(NO₃)₂.4H₂O methanol/ 70.59 72.75 87.14 10.102 14.412 14.964 P-1 0.06 mmol CHP H₂(HPDC) H₂O 0.06 mmol Tb(PDC)1.5 Tb(NO₃)₃.5H₂O DMF 109.8 103.61 100.14 9.829 12.11 14.628 P-1 0.21 mmol H₂O/ H₂(PDC) ethanol 0.034 mmol ZnDBP Zn(NO₃)₂.6H₂O MeOH 90 93.67 90 9.254 10.762 27.93 P2/n 0.05 mmol dibenzylphosphate 0.10 mmol Zn₃(BPDC) ZnBr₂ DMF 90 102.76 90 11.49 14.79 19.18 P21/n 0.021 mmol 4,4‘BPDC 0.005 mmol CdBDC Cd(NO₃)₂.4H₂O DMF 90 95.85 90 11.2 11.11 16.71 P21/n 0.100 mmol Na₂SiO₃ H₂(BDC) (aq) 0.401 mmol Cd-mBDC Cd(NO₃)₂.4H₂O DMF 90 101.1 90 13.69 18.25 14.91 C2/c 0.009 mmol MeNH₂ H₂(mBDC) 0.018 mmol Zn₄OBNDC Zn(NO₃)₂.6H₂O DEF 90 90 90 22.35 26.05 59.56 Fmmm 0.041 mmol MeNH₂ BNDC H₂O₂ Eu(TCA) Eu(NO₃)₃.6H₂O DMF 90 90 90 23.325 23.325 23.325 Pm-3n 0.14 mmol chloro- TCA benzene 0.026 mmol Tb(TCA) Tb(NO₃)₃.6H₂O DMF 90 90 90 23.272 23.272 23.372 Pm-3n 0.069 mmol chloro- TCA benzene 0.026 mmol Formate Ce(NO₃)₃.6H₂O H₂O 90 90 120 10.668 10.667 4.107 R-3m 0.138 mmol ethanol Formic acid 0.43 mmol FeCl₂.4H₂O DMF 90 90 120 8.2692 8.2692 63.566 R-3c 5.03 mmol Formic acid 86.90 mmol FeCl₂.4H₂O DEF 90 90 90 9.9364 18.374 18.374 Pbcn 5.03 mmol Formic acid 86.90 mmol FeCl₂.4H₂O DEF 90 90 90 8.335 8.335 13.34 P-31c 5.03 mmol Formic acid 86.90 mmol NO330 FeCl₂.4H₂O form- 90 90 90 8.7749 11.655 8.3297 Pnna 0.50 mmol amide Formic acid 8.69 mmol NO332 FeCl₂.4H₂O DIP 90 90 90 10.0313 18.808 18.355 Pbcn 0.50 mmol Formic acid 8.69 mmol NO333 FeCl₂.4H₂O DBF 90 90 90 45.2754 23.861 12.441 Cmcm 0.50 mmol Formic acid 8.69 mmol NO335 FeCl₂.4H₂O CHF 90 91.372 90 11.5964 10.187 14.945 P21/n 0.50 mmol Formic acid 8.69 mmol NO336 FeCl₂.4H₂O MFA 90 90 90 11.7945 48.843 8.4136 Pbcm 0.50 mmol Formic acid 8.69 mmol NO13 Mn(Ac)₂.4H₂O ethanol 90 90 90 18.66 11.762 9.418 Pbcn 0.46 mmol Bezoic acid 0.92 mmol Bipyridine 0.46 mmol NO29 Mn(Ac)₂.4H₂O DMF 120 90 90 14.16 33.521 33.521 P-1 MOF-0 like 0.46 mmol H₃BTC 0.69 mmol Mn(hifac)₂ Mn(Ac)₂.4H₂O ether 90 95.32 90 9.572 17.162 14.041 C2/c (O₂CC₆H₅) 0.46 mmol Hfac 0.92 mmol Bipyridine 0.46 mmol BPR43G2 Zn(NO₃)₂.6H₂O DMF 90 91.37 90 17.96 6.38 7.19 C2/c 0.0288 mmol CH₃CN H₂BDC 0.0072 mmol BPR48A2 Zn(NO₃)₂6H₂O DMSO 90 90 90 14.5 17.04 18.02 Pbca 0.012 mmol toluene H₂BDC 0.012 mmol BPR49B1 Zn(NO₃)₂6H₂O DMSO 90 91.172 90 33.181 9.824 17.884 C2/c 0.024 mmol methanol H₂BDC 0.048 mmol BPR56E1 Zn(NO₃)₂6H₂O DMSO 90 90.096 90 14.5873 14.153 17.183 P2(1)/n 0.012 mmol n-propanol H₂BDC 0.024 mmol BPR68D10 Zn(NO₃)₂6H₂O DMSO 90 95.316 90 10.0627 10.17 16.413 P2(1)/c 0.0016 mmol benzene H₃BTC 0.0064 mmol BPR69B1 Cd(NO₃)₂4H₂O DMSO 90 98.76 90 14.16 15.72 17.66 Cc 0.0212 mmol H₂BDC 0.0428 mmol BPR73E4 Cd(NO₃)₂4H₂O DMSO 90 92.324 90 8.7231 7.0568 18.438 P2(1)/n 0.006 mmol toluene H₂BDC 0.003 mmol BPR76D5 Zn(NO₃)₂6H₂O DMSO 90 104.17 90 14.4191 6.2599 7.0611 Pc 0.0009 mmol H₂BzPDC 0.0036 mmol BPR80B5 Cd(NO₃)₂.4H₂O DMF 90 115.11 90 28.049 9.184 17.837 C2/c 0.018 mmol H₂BDC 0.036 mmol BPR80H5 Cd(NO₃)₂4H₂O DMF 90 119.06 90 11.4746 6.2151 17.268 P2/c 0.027 mmol H₂BDC 0.027 mmol BPR82C6 Cd(NO₃)₂4H₂O DMF 90 90 90 9.7721 21.142 27.77 Fdd2 0.0068 mmol H₂BDC 0.202 mmol BPR86C3 Cd(NO₃)₂6H₂O DMF 90 90 90 18.3449 10.031 17.983 Pca2(1) 0.0025 mmol H₂BDC 0.075 mmol BPR86H6 Cd(NO₃)₂.6H₂O DMF 80.98 89.69 83.412 9.8752 10.263 15.362 P-1 0.010 mmol H₂BDC 0.010 mmol Co(NO₃)₂6H₂O NMP 106.3 107.63 107.2 7.5308 10.942 11.025 P1 BPR95A2 Zn(NO₃)₂6H₂O NMP 90 102.9 90 7.4502 13.767 12.713 P2(1)/c 0.012 mmol H₂BDC 0.012 mmol CuC₆F₄O₄ Cu(NO₃)₂.2.5H₂O DMF 90 98.834 90 10.9675 24.43 22.553 P2(1)/n 0.370 mmol chloro- H₂BDC(OH)₂ benzene 0.37 mmol Fe Formic FeCl₂.4H₂O DMF 90 91.543 90 11.495 9.963 14.48 P2(1)/n 0.370 mmol Formic acid 0.37 mmol Mg Formic Mg(NO₃)₂.6H₂O DMF 90 91.359 90 11.383 9.932 14.656 P2(1)/n 0.370 mmol Formic acid 0.37 mmol MgC₆H₄O₆ Mg(NO₃)₂.6H₂O DMF 90 96.624 90 17.245 9.943 9.273 C2/c 0.370 mmol H₂BDC(OH)₂ 0.37 mmol ZnC₂H₄BDC ZnCl₂ DMF 90 94.714 90 7.3386 16.834 12.52 P2(1)/n MOF-38 0.44 mmol CBBDC 0.261 mmol MOF-49 ZnCl₂ DMF 90 93.459 90 13.509 11.984 27.039 P2/c 0.44 mmol CH3CN m-BDC 0.261 mmol MOF-26 Cu(NO₃)₂.5H₂O DMF 90 95.607 90 20.8797 16.017 26.176 P2(i)/n 0.084 mmol DCPE 0.085 mmol MOF-112 Cu(NO₃)₂.2.5H₂O DMF 90 107.49 90 29.3241 21.297 18.069 C2/c 0.084 mmol ethanol o-Br-m-BDC 0.085 mmol MOF-109 Cu(NO₃)₂.2.5H₂O DMF 90 111.98 90 23.8801 16.834 18.389 P2(1)/c 0.084 mmol KDB 0.085 mmol MOF-111 Cu(NO₃)₂.2.5H₂O DMF 90 102.16 90 10.6767 18.781 21.052 C2/c 0.084 mmol ethanol o-BrBDC 0.085 mmol MOF-110 Cu(NO₃)₂.2.5H₂O DMF 90 90 120 20.0652 20.065 20.747 R-3/m 0.084 mmol thiophene dicarboxylic 0.085 mmol MOF-107 Cu(NO₃)₂.2.5H₂O DEF 104.8 97.075 95.206 11.032 18.067 18.452 P-1 0.084 mmol thiophene dicarboxylic 0.085 mmol MOF-108 Cu(NO₃)₂.2.5H₂O DBF/ 90 113.63 90 15.4747 14.514 14.032 C2/c 0.084 mmol methanol thiophene dicarboxylic 0.085 mmol MOF-102 Cu(NO₃)₂.2.5H₂O DMF 91.63 106.24 112.01 9.3845 10.794 10.831 P-1 0.084 mmol H₂(BDCCl₂) 0.085 mmol Clbdc1 Cu(NO₃)₂.2.5H₂O DEF 90 105.56 90 14.911 15.622 18.413 P-1 0.084 mmol H₂(BDCCl₂) 0.085 mmol Cu(NMOP) Cu(NO₃)₂2.5H₂O DMF 90 102.37 90 14.9238 18.727 15.529 P2(1)/m 0.084 mmol NBDC 0.085 mmol Tb(BTC) Tb(NO₃)₃.5H₂O DMF 90 106.02 90 18.6986 11.368 19.721 0.033 mmol H₃BTC 0.033 mmol Zn₃(BTC)₂ ZnCl₂ DMF 90 90 90 26.572 26.572 26.572 Fm-3m Honk 0.033 mmol ethanol H₃BTC 0.033 mmol Zn₄O(NDC) Zn(NO₃)₂.4H₂O DMF 90 90 90 41.5594 18.818 17.574 aba 0.066 mmol ethanol 14NDC 0.066 mmol CdTDC Cd(NO₃)₂.4H₂O DMF 90 90 90 12.173 10.485 7.33 Pmma 0.014 mmol H₂O thiophene 0.040 mmol DABCO 0.020 mmol IRMOF-2 Zn(NO₃)₂.4H₂O DEF 90 90 90 25.772 25.772 25.772 Fm-3m 0.160 mmol o-Br-BDC 0.60 mmol IRMOF-3 Zn(NO₃)₂.4H₂O DEF 90 90 90 25.747 25.747 25.747 Fm-3m 0.20 mmol ethanol H₂N—BDC 0.60 mmol IRMOF-4 Zn(NO₃)₂.4H₂O DEF 90 90 90 25.849 25.849 25.849 Fm-3m 0.11 mmol [C₃H₇O]₂—BDC 0.48 mmol IRMOF-5 Zn(NO₃)₂.4H₂O DEF 90 90 90 12.882 12.882 12.882 Pm-3m 0.13 mmol [C₅H₁₁O]₂—BDC 0.50 mmol IRMOF-6 Zn(NO₃)₂.4H₂O DEF 90 90 90 25.842 25.842 25.842 Fm-3m 0.20 mmol [C₂H₄]—BDC 0.60 mmol IRMOF-7 Zn(NO₃)₂.4H₂O DEF 90 90 90 12.914 12.914 12.914 Pm-3m 0.07 mmol 1,4NDC 0.20 mmol IRMOF-8 Zn(NO₃)₂.4H₂O DEF 90 90 90 30.092 30.092 30.092 Fm-3m 0.55 mmol 2,6NDC 0.42 mmol IRMOF-9 Zn(NO₃)₂.4H₂O DEF 90 90 90 17.147 23.322 25.255 Pnnm 0.05 mmol BPDC 0.42 mmol IRMOF-10 Zn(NO₃)₂.4H₂O DEF 90 90 90 34.281 34.281 34.281 Fm-3m 0.02 mmol BPDC 0.012 mmol IRMOF-11 Zn(NO₃)₂.4H₂O DEF 90 90 90 24.822 24.822 56.734 R-3m 0.05 mmol HPDC 0.20 mmol IRMOF-12 Zn(NO₃)₂.4H₂O DEF 90 90 90 34.281 34.281 34.281 Fm-3m 0.017 mmol HPDC 0.12 mmol IRMOF-13 Zn(NO₃)₂.4H₂O DEF 90 90 90 24.822 24.822 56.734 R-3m 0.048 mmol PDC 0.31 mmol IRMOF-14 Zn(NO₃)₂.4H₂O DEF 90 90 90 34.381 34.381 34.381 Fm-3m 0.17 mmol PDC 0.12 mmol IRMOF-15 Zn(NO₃)₂.4H₂O DEF 90 90 90 21.459 21.459 21.459 Im-3m 0.063 mmol TPDC 0.025 mmol IRMOF-16 Zn(NO₃)₂.4H₂O DEF 90 90 90 21.49 21.49 21.49 Pm-3m 0.0126 mmol NMP TPDC 0.05 mmol

ADC Acetylene dicarboxylic acid NDC Naphtalene dicarboxylic acid BDC Benzene dicarboxylic acid ATC Adamantane tetracarboxylic acid BTC Benzene tricarboxylic acid BTB Benzene tribenzoate MTB Methane tetrabenzoate ATB Adamantane tetrabenzoate ADB Adamantane dibenzoate

Examples for the synthesis of these materials as such can, for example, be found in: J. Am. Chem. Soc. 123 (2001) pages 8241ff or in Acc. Chem. Res. 31 (1998) pages 474ff, which are fully encompassed within the content of the present application with respect to their respective content.

The separation of the framework materials, particularly of MOF-5, from the mother liquor of the crystallization may be achieved by procedures known in the art such as solid-liquid separations, centrifugation, extraction, filtration, membrane filtration, cross-flow filtration, flocculation using flocculation adjuvants (non-ionic, cationic and anionic adjuvants) or by the addition of pH shifting additives such as salts, acids or bases, by flotation, as well as by evaporation of the mother liquor at elevated temperature and/or in vacuo and concentrating of the solid. The material obtained in this step is typically a fine powder and cannot be used for most practical applications, e.g. in catalysis, where shaped bodies are required.

The invention is now further described by way of the following examples, which are, however, not meant to limit the scope of the present application.

EXAMPLE 1 Preparation of a Catalyst According to the Invention

The following materials were used to prepare one catalyst according to the invention, containing MOF-5 as the porous material and Ag as an active metal:

Starting Molar Material Amount Calculated Experimental AgNO₃ 25.9 mmol 4.3 g 4.4 g DEF 904.6 mmol 91.5 g 91.5 g MOF-5 4.2 g 4.2 g acetontrile 33.0 g 33.0 g

The AgNO₃ (Merck) is dissolved in DEF (diethylformamide) and acetonitrile in a beaker. This clear solution is then added to an autoclave (250 ml volume) which already contains the MOF-5.

The crystallization occurred at 60° C. and within twenty hours. Subsequently, the solution was cooled and the solvent was decanted from the black crystals. Said crystals were washed in chloroforme until the chloroforme almost showed no color anymore. The catalyst was dried in vacuo until no more change in weigth occured. The yield is 4.7 g with a silver content of 15.3% by weight.

Example 2 Using the Catalyst from Example 1 for the catalysis of epoxidation reactions

In a gas phase flow apparatus (tubular reactor with 9 mm inner diameter, 150 mm reactor length), 500 mg of the catalyst prepared according to Example 1 are filled as a micro fixed bed. A mixture of oxygen, helium and propylene in the volume ratio of 66:24:10 is streamed over the catalyst at a temperature of 220° C. The effluent stream is analyzed by means of gas chromatography.

After a running time of 10 hours, the turnover with respect to propylene is 4.3% with the selectivity with respect to propylene oxide being 8.2%. After 15 hours, a turnover of 3.3% at a selectivity of 10.3% is obtained. 

What is claimed is:
 1. A process for the epoxidation of organic compounds, comprising reacting at least one organic compound with at least one epoxidizing agent in the presence of a catalyst, wherein the catalyst comprises a porous metal-organic framework material comprising at least one metal ion and at least one at least bidentate organic compound which is coordinately bound to said metal ion.
 2. The process according to claim 1, wherein said epoxidizing agent is selected from the group consisting of a hydroperoxide, O₂, ozone, nitric oxides, and reactive oxides.
 3. The process according to claim 2, wherein the hydroperoxide is selected from the group consisting of hydrogen peroxide, ethylbenzene peroxide, and cumenehydroperoxide.
 4. The process according to claim 1, wherein said organic compound has at least one C—C double bond.
 5. The process according to claim 4, wherein said organic compound with at least one C—C double bond is an alkene having 2 to 8 carbon atoms.
 6. The process according to claim 1, wherein the metal ion is selected from the group consisting of Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Sc³⁺, Y³⁺, Ti⁴⁺, Zr⁴⁺, Hf⁴⁺, V⁴⁺, V³⁺, V²⁺, Nb³⁺, Ta³⁺, Cr³⁺, Mo³⁺, W³⁺, Mn³⁺, Mn²⁺, Re³⁺, Re²⁺, Fe³⁺, Fe²⁺, Ru³⁺, Ru²⁺, Os³⁺, Os²⁺, Co³⁺, Co²⁺, Rh²⁺, Rh⁺, Ir²⁺, Ir⁺, Ni²⁺, Ni⁺, Pd²⁺, Pd⁺, Pt²⁺, Pt⁺, Cu²⁺, Cu⁺, Ag⁺, Au⁺, Zn²⁺, Cd²⁺, Hg²⁺, Al³⁺, Ga³⁺, In³⁺, Tl³⁺, Si⁴⁺, Si²⁺, Ge⁴⁺, Ge²⁺, Sn⁴⁺, Sn²⁺, Pb⁴⁺, Pb²⁺, As⁵⁺, As³⁺, As⁺, Sb⁵⁺, Sb³⁺, Sb⁺, Bi⁵⁺, Bi³⁺, Bi⁺.
 7. The process according to claim 5, wherein said alkene is selected from the group consisting of ethene, propene, 1-butene, 2-butene, isobutene, butadiene, pentene, and hexenes.
 8. The process according to claim 1, wherein said organic compound is selected from the group consisting of ethene, propene, 1-butene, 2-butene, isobutene, butadiene, pentene, piperylene, hexenes, hexadienes, heptenes, octenes, diisobutene, trimethylpentene, nonenes, dodecene, tridecene, tetradecene, eicosene, tripropene, tetrapropene, polybutadienes, polyisobutenes, isoprenes, terpenes, geraniol, linalool, linalyl acetate, methylenecyclopropane, cyclopentene, cyclohexene, norbornene, cycloheptene, vinylcyclohexane, vinyloxiran, vinylcyclohexene, styrene, cyclooctene, cyclooctadiene, vinylnorbornene, indene, tetrahydroindene, methylstyrene, dicyclopentadiene, dinvinylbenzene, cyclododecene, cyclododecatriene, stilbene, diphenylbutadiene, vitamin A, beta-carotene, vinylidene fluoride, allylhalides, crotyl chloride, methallyl chloride, dichlorobutene, allyl alcohol, methallyl alcohol, butenols, butenediols, cyclopentenediols, pentenols, octadienols, tridecenols, unsaturated steroids, ethoxyethene, isoeugenol, anethole, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, vinylacetic acid, unsaturated fatty acids such as oleic acid, linoleic acid, palmitic acid, naturally occurring fats and oils.
 9. The process according to claim 1, wherein the metal-organic framework material is microporous.
 10. The process according to claim 1, wherein the metal-organic framework material is mesoporous.
 11. The process according to claim 1, wherein the bidentate organic compound has a functional group selected from the group consisting of CO₂H, CS₂H, NO₂, SO₃H, Si(OH)₃, Ge(OH)₃, Sn(OH)₃, Si(SH)₄, Ge(SH)₄, Sn(SH)₃, PO₃H, AsO₃H, AsO₄H, P(SH)₃, As(SH)₃, CH(RSH)₂, C(RSH)₃, CH(RNH)₂, C(RNH₂)₃, CH(ROH)₂, C(ROH)₃, CH(RCN)₂, C(RCN)₃, wherein R is an alkyl group having from 1 to 5 carbon atoms, or an aryl group consisting of 1 to 2 phenyl rings, and CH(SH)₂, C(SH)₃, CH(NH₂)₂, C(NH₂)₂, CH(OH)₂, C(OH)₃, CH(CN)₂ and C(CN)₃.
 12. The process according to claim 1, wherein the bidentate organic compound is selected from the group consisting of 1,3,5-benzene tricarboxylate, acetylene dicarboxylate, naphtalen dicarboxylate, benzene dicarboxylate, adamantane tetracarboxylate, benzene tricarboxylate, benzene tribenzoate, methane tetrabenzoate, and adamantane tribenzoate.
 13. The process according to claim 1, wherein the metal-organic framework material further comprises at least one monodentate ligand.
 14. The process according to claim 1, wherein the monodentate ligand is selected from the group consisting of alkyl amines and ammonium salts therof; aryl amines and ammonium salts therof; alkyl phosphonium salts; aryl phosphonium salts; alkyl organic acids and salts thereof; aryl organic acids and salts thereof; aliphatic alcohols; aryl alcohols; inorganic sufates, nitrates, nitrites, sulfites, phosphates, hydrogen phosphates, dihydrogen phosphates, diphosphates, triphosphates, phosphites, chlorides, chlorates, bromides, bromates, iodides, iodates, carbonates, bicarbonates, and salts or acids thereof; ammonia, carbon dioxide, methane, oxygen, ethylene, hexane, benzene, toluene, xylene, chlorobenzene, nitrobenzene, naphthalene, thiophene, pyridine, acetone, 1,2-dichloroethane, methylene chloride, tetrahydrofuran, ethanolamine, thriethylamine, and trifluoromethylsulfonic acid.
 15. The process according to claim 1, wherein the metal ion is Zn⁺ and the bidentate organic compound is terphthalic acid.
 16. The process according to claim 1, wherein the pores of the metal-organic framework have a size in the range of from 0.2 to 30 nm.
 17. The process according to claim 16, wherein the pores of the metal-organic framework have a size in the range of from 0.3 to 3 nm.
 18. The process according to claim 1, wherein the catalyst further comprises an active metal. 